Combustion process and fuel compositions

ABSTRACT

The invention disclosed herein is directed to an improved combustion process whereby the fuel is efficiently utilized and the formation of undesirable exhaust smoke is reduced. The combustion process comprises the burning of a fuel in which there is incorporated a small amount of metal salts having a particle size less than about 800 microns. The invention relates further to improved fuel compositions containing such metal salts.

United States Patent [191 Le Suer Mar. 19, 1974 COMBUSTION PROCESS ANDFUEL [58] Field of Search 44/51, 57, 66, 70, 76

COMPOSITIONS [75] Inventor: William Monroe Le Suer, Cleveland, [56]References Cited Ohio UNITED STATES PATENTS Assigneez The Lubrizolcorporafion 3,637,356 1/1972 Vanderlinden et al. 44/51 Wickliffe, OhioPrimary Examiner-Daniel E. Wyman [22] June 1971 Assistant Examiner-W. J.Shine [21] Appl. No.: 151,538 Attorney, Agent, or Firm-Adams, Jr. JamesW.

Related US. Application Data 5 ABSTR C [63] Continuation of Ser. No.89,031. Nov. 12, 1970,

aband ned, which is a c ntin i of s The invention disclosed herein isdirected to an im- 700,301, Jan. 24, 1968, abandoned, which is a provedcombustion process whereby the fuel is efficontinuation-in-part of Ser.Nos. 474,479, July 23, ciently utilized and the formation of undesirableexl965 abandoned, and 468,558, P haust smoke is reduced. The combustionprocess coml965- abmdmed f 9 SePtprises the burning of a fuel in whichthere is incorpo- 532 5 :2 a gomlguauon of rated a small amount of metalsalts having a particle ep a an one size less than about 800 microns.The invention relates 52 us. Cl 44/51, 44/57, 44/66, f ggf gfi fuel Such44/70, 44/76 [51] Int. Cl. Cl0l 1/18, ClOl 1/30, C101 1/32 22 Claims, N0Drawings COMBUSTION PROCESS AND FUEL COMPOSITIONS This application is acontinuation of copending application Ser. No. 89,031, filed Nov. 12,1970 now abandoned, which, in turn, is a continuation of applicationSer. No. 700,301, filed Jan. 24, 1968 which is a continuation-in-part ofabandoned application Ser. No. 474,479, filed July 23, 1965; Ser. No.486,558, filed Sept. 10, 1965; and Ser. No. 665,934, filed Sept. 6,1967, the last being a continuation of earlier filed application Ser.No. 394,337, filed Sept. 3, 1964, the latter five applications nowabandoned.

This invention relates to the operation of internal combustion engines.in a more particular sense it relates to improved operation of dieseland jet engines which tend to produce black exhaust smoke.

Diesel and jet engines performing under severe service conditions suchas occur in the operation of heavy automotive equipment, ships andtrucks have a tendency to produce black exhaust smoke, especially onrapid acceleration of the engine. The smoke creates a problem of airpollution and in many localities it constitutes a violation of the locallaw to so pollute the air.

Accordingly, it is a principal object of this invention to provide animproved method of operating diesel and jet engines.

It is also an object of this invention to provide an improved method ofoperating diesel and jet engines whereby the formation of black exhaustsmoke is minimized. A

It is also an object of this invention to provide improved fuelcompositions useful for operating internal combustion engines, and inparticular, diesel and jet engines.

These and other objects are attained in accordance with this inventionby providing a combustion process involving the burning of a diesel orjet fuel in an internal combustion engine tending to produce smoke,which comprises burning said fuel in the presence of at least about 0.01percent by weight ofa metal salt of an inorganic acid selected from theclass consisting of carbonic, sulfurous, and sulfuric acids, wherein themetal is a Group I or Group 11 metal, said metal salt having a particlesize less than about 800 microns.

The above metal salts are effective as smokesuppressing agents in theprocess. The physical state and the chemical composition of theparticular metal salt during combustion are critical to itseffectiveness in reducing the formation of black smoke in the engine. Itmust be of relatively small particle size, e.g., less than about 800microns. In general, a metal salt having a smaller particle size ispreferred and one having an average particle size from about 0.0004 toabout 50 microns is especially desirable. Further, it must be in therequired finely divided form at the time when the combustion of the fueltakes place. The physical state of the smoke suppressing agent prior tothat time is not critical. Thus, the smoke suppressing agent may be in afluid form or agglomerated solid form of large particle size beforecombustion takes place. For instance, it may be dissolved or dispersedin a liquid carrier or mechanically mixed with the carrier before it isintroduced into the combustion zone. It may further be chemicallycombined with another substance in the form of a chemical complex whichis capable of releasing the smoke suppressing agent in the desiredparticle size during combustion of the fuel.

To be effective, the metal salt must be present at a concentration of atleast about 0.01 percent by weight of the fuel being burned in thecombustion chamber. lts concentration may be as high as 5 percent byweight of the fuel or even higher. In the case of polymeric metal saltadditive such as is described hereinbelow, the effective concentrationof the smoke suppressing agent should be at least about 0.1 percent; itmay be as high as about 5 percent or higher, but is usually less thanabout 2 percent by weight of the fuel.

The metal salt, as indicated previously, comprises a Group I or Group IImetal salt of an inorganic acid such as carbonic, sulfurous, or sulfuricacid. It includes principally carbonates, sulfites, and sulfates of themetal although it may include also bicarbonates, bisulfites, etc. Themetal is illustrated by lithium, potassium, sodium, copper, magnesium,zinc. cadmium, strontium, calcium or barium. Calcium and barium salts ofcarbonic acid are preferred. Mixtures of metal salts likewise areuseful.

The metal salt may be either monomeric or polymeric. The term monomeric.salt is used to designate ordinary, inorg'anic metal salts such as NaCONa SO Na SO CuSO,, Cu SO.,, ZnCO BaCO and CaSO The term polymeric saltis used to designate a salt characterized by the molecular structure ofa polymeric metal salt unit attached to an oleophilic group such as ispresent in A-( M-O-Y-Q) ,,B wherein M is a Group 1 or Group 11 metal, Yis As indicated previously, the polymeric unit is attached to at leastone acidic oleophilic group as an end group. The oleophilic groupusually contains at least about eight aliphatic carbon atoms and maycontain as many as 400 or more aliphatic carbon atoms. It is illustratedby the anionic group derived from an oil-soluble sulfonic acid,carboxylic acid, phosphonic acid, phosphinic acid, enols, alcohols, etc.

The oil-soluble sulfonic acids from which the oleophilic group may bederived are illustrated by an alkyl sulfonic acid or alkaryl sulfonicacid having at least 12 aliphatic carbon atoms in the alkyl radical. Itmay be, for example, mahogany sulfonic acid, dodecyl benzene sulfonicacid, di(dodecyl)benzene sulfonic acid, dodecylnaphthalene sulfonicacid, bright stock sulfonic acid, tetra(tridecyl)benzene sulfonic acid,octadecylbenzene sulfonic acid, polypropene(molecular weight ofl,500)-substituted benzene sulfonic acid, polybutene(molecular weight of5,000)-substituted benzene sulfonic acid, etc.

The oil-soluble phosphonic or phosphinic acids may be hydrocarbonsubstituted oxyphosphonic or oxyphosphinic acids or the correspondingthio analogs thereof such as thiophosphonic, monothiophosphinic ordithiophosphinic acids wherein the hydrocarbon substituent may be alkylor alkaryl having at least about 12 aliphatic carbon atoms in the alkylradical. Specific examples include polybutenyl(molecular weight ofl,O)-phosphonic acid, dipolyisobutenyl(molecular weight of750)-phosphinic acid, dipolyisobutenyl(- molecular weight of l,500)-phosphinomonothioic acid, dipolypropenyl(molecular weight of2,000)- phosphinodithioic acid, didodecylphosphinodithioic.

acid, dioctadecylphosphinodithioic acid or mixtures of acids such as arederived by the reaction of an olefin polymer (e.g., polyethylene,polypropylene, polybutene, copolymer of isobutene and styrene) with aphosphorizing agent such as phosphorus pentasulfide, phosphorusheptasulfide, phosphorus sesquisulfide, phosphorus pentoxide, phosphorusoxychloride, phosphorus trichloride and sulfur, phosphorus trichiorideand oxygen, phosphorus and sulfur dichloride, phosphorus and sulfurmonochloride, phosphorus oxysulfide, phosphorus oxybromide, etc.

A useful class of oil-soluble phosphorus acids comprises acidicphosphorized aliphatic or alkyl aromatic hydrocarbons, with thealiphatic hydrocarbons being preferred. Such hydrocarbons include, forexample, the white oils and other liquid petroleum oils having at leastabout l2 carbon atoms and include also synthetic hydrocarbons such asare obtained by the reduction of fatty oils. Also included, andpreferred, are the olefin polymers having molecular weights betweenabout 150 and 48,000, especially about 5003,000. These includehomopolymers and copolymers of mono-olefins having from two to 12 carbonatoms, e.g., ethylene, l-hexene, l-octene, Z-methyl-l-heptene,3-cyclohexyl-l-butene, l-decene, 2-methyl-5-propyl-l-hexene, etc. Alsouseful are the interpolymers of such mono-olefins with otherinterpolymerizable olefinic substances such as aromatic olefins,cycloaliphatic olefins, and polyolefins. These interpolymers include,for example, those prepared by polymerizing isobutene with styrene;isobutene with butadiene; propene with isoprene; ethylene withpiperylene; isobutene with chloroprene; isobutene with p-methylstyrene;l-hexene with 1,3-hexadiene; isobutene with styrene and piperylene; andthe like.

The relative proportions of the mono-olefins to the other olefinicmonomers in the interpolymers may vary within wide ranges provided thatthe polyolefin, if used, is not present in sufficiently high proportionsas to cause substantial crosslinking and insolubility. Specific examplesof the useful interpolymers include the copolymer of 95 percent (byweight) of isobutene with 5 percent of styrene; the terpolymer of 98percent of isobutene with 1 percent of piperylene and 1 percent ofchloroprene; the terpolymer of 95 percent of isobutene with 2 percent ofl-butene and 3 percent of l-hexene; the terpolymer of 60 percent ofisobutene with percent of l-pentene and 20 percent of l-octene; thecopolymer of 80 percent of l-hexene and 20 percent of l -heptene; theterpolymer of 90 percent of isobutene with 2 percent of cyclohexene and8 percent of propene; and the copolymer of percent of ethylene and 20percent of propene.

The olefin polymer may be phosphorized by treatment with such reagentsasphosphorus sulfides, phosphorus halides, phosphorus oxyhalide,phosphorus thiohalides, chlorine and a phosphorus trihalide, sulfur andyellow phosphorus, sulfur and a phosphorus trihalide, or yellowphosphorus and a sulfur halide. Various techniques for phosphorizationare known. A commonly used method involves simply mixing the hydrocarbonwith the phosphorizing agent at the desired temperature, usually above80C. and preferably between and 300C. Another method consists ofchlorinating the olefin polymer and reacting the chlorinated polymerwith a phosphorizing agent.

The amount of the phosphorizing agent to be used depends upon the natureof the product desired. For most applications involving phosphorizationof olefin polymers, products having a phosphorus content from 0.05 to 10percent, usually from 0.1 to 5 percent, are desirable. Thus, therelative proportion of the phosphorizing agent to be used is such as toprovide from about 0.05 to 10 parts (by weight), preferably from 0.1 to'5 parts, of phosphorus per 100 parts of the olefin polymer in thereaction mixture. In most instances, from 0.1 part to 50 parts of thephosphorizing agent is used per 100 parts of the olefin polymer.

The oil-soluble carboxylic acids are illustrated by mono-carboxylicacids such as dodecanoic acid, octadecanoic acid, hexatriacontanoicacid, oleic acid, stearic acid, oleostearic acid, linoleic acid,myristic acid, xylylstearic acidydodecylbenzoic acid, di(octadecyl)-naphthoic acid, naphthenic acid, or other fatty acids having at leastabout 12 aliphatic carbon atoms in the molecule. Polycarboxylic acidssuch as alkylor alkenyl succinic acids wherein the alkyl or all-tenylsubstituent has from about 12 to 500 aliphatic. carbon atoms areuseful.They are exemplified by polyisobutene(molecular weight ofl,0O0)-substituted succinic acid, polypropene(molecular weight of700)-substituted succinic acid.

The oil-soluble enols should contain at least about l2,and preferablyless than about 30, aliphatic carbon atoms, They may be tautomericaldehydes or ketones, i.e., carbonyl compounds having at least onehydrogen substituent present in the carbon atom adjacent to the carbonylgroup. Examples of such tautomeric ketones and aldehydes include methyldodecyl ketone, dihexyl ketone, ethyl octadecyl ketone, dodecylaldehyde, behenyl aldehyde, dicyclohexyl ketone, etc.

The oil-soluble alcohols should contain at least about eight, andpreferably less than about 30, aliphatic carbon atoms. They areillustrated by octanol, ethylcyclohexanol, dodecanol, octadecanol,behenyl alcohol, hexatriacontanol, 9-phenyloctadecanol, etc.

it will be noted that the terms hydrocarbon, alkyl, and alkaryl as theyare used herein, describe sustances or groups which are essentiallyhydrocarbon in character. They may contain polar or nonhydrocarbonsubstituents provided that such substituents are not present inproportions so as to alter significantly the hydrocarbon character ofthe substance or group. The non-hydrocarbon substituents are exemplifiedby chloro, bromo, ether, keto, aldehydo, or iodo radicals. The upperlimit of the proportion of such substituents in a hydrocarbon or ahydrocarbon group in most substances is about percent by weight of thehydrocarbon portion of the substance or group.

The polymeric metal salt may be prepared by a variety of methods.Ordinarily it is obtained by treating an oleophilic substance from whichthe oleophilic group of the polymeric metal salt is derived, with anexcess of a Group I or Group II metal base and an acidic gas such ascarbon dioxide, sulfur dioxide or sulfur trioxide under conditionsfavorable to the formation of homogeneous basic complex. Such conditionsusually include a temperature of from about 50 to 300C or a highertemperature; the use of a promoter, i.e., one capable of facilitatingthe incorporation of the metal base into the oleophilic substance; andintimate mixing of the reactants for a period of time sufficient to formthe homogeneous, basic complex.

The metal base useful in preparing the polymeric metal salt of thisinvention may be the bicarbonate, carbonate, oxide, hydroxide, hydride,lower alcoholate (i.e., derived from an alcohol having up to about sixcarbon atoms, such as methyl, ethyl, and isopropyl alcohols) of a GroupI or Group II metal such as illustrated previously. The oxides andhydroxides of Group II metals, especially calcium or barium, arepreferred.

The promoters used in preparing the polymeric metal salts are known inthe art. The preferred ones are alcohols. They may be mercaptans,amines, aci-nitro compounds, or enolic compounds. The alcohols useful asthe promoting agent include, for example, methanol, ethanol,isopropanol, cyclohexanol, decanol, dodecanol, behenyl alcohol, ethyleneglycol, diethylene glycol, triethylene glycol, monomethyl ether ofethylene glycol, trimethylene glycol, hexamethylene glycol, glycerol,pentaerythritol, benzyl alcohol, phenylethyl alcohol. Other compoundsuseful as the promoting agent are illustrated by ethyl acetoacetate,acetylacetone, acetamide, ethanolamine, diethanolamine, triethanolamine,nitro-methane, nitro-propane, nitro-decane, ni-

trobenzene, nitro-toluene, methylamine, dimethylamine, aniline,phenylenediamine, N,N- dimethylphenylenediamine, toluidine,cyclohexylamine, N-methyl decylamine, naphthylamine, thiophenol, methylmercaptan, dodecyl mercaptan, isooctyl mercaptan, benzyl mercaptan, etc.Also contemplated are polymeric metal salts in which the oleophilicgroup is a carboxylic or phosphorus group such as described above whichare prepared with phenols as the promoter.

A particularly useful method for preparing the polymeric metal saltinvolves preparing a mixture of an oleophilic substance and astoichiometric excess of a metal base and treating the mixture at thedesired temperature with an acidic gas until a homogeneous product isobtained. The process is carried out at a temperature from about 50 toabout 300C or any temperature below the decomposition point of thereaction mixture. The process is carried out preferably in the presenceof a solvent or diluent such as mineral oil, benzene, xylene, dioxane,chloroform or naphtha. An especially useful solvent is one having a lowpour point, such as halo-aryl or alkaryl hydrocarbon, e.g.,chlorobenzene, p-cymene, mesitylene, etc. As the treatment with theacidic gas proceeds, the metal base is converted to the correspondingpolymeric carbonat, sulfite or sulfate and forms a complex with theoleophilic stubstance. The product is a homogeneous complex which, forthe purpose of this invention, is conveniently described as a polymericmetal salt because of the presence in its molecular structure of thepolymeric unit -(M-O-Y- O),,-, described previously. It should be notedthat where a Group I metal is used in preparing the polymeric metalsalt, it is believed that the metal depends for the formation of thecomplex on both primary and secondary valences and thus behaves as adivalent metal.

In many instances it is not necessary for all of the metal base presentin the process mixture to be converted by the treatment with the acidicgas to a carbonate, sulfite, or sulfate complex. A homogeneous polymericmetal salt is often obtained when as little as about percent of themetal base is converted by treatment with the acidic gas and such saltis contemplated for use in this invention.

The amount of the metal present in the polymeric metal salt is criticalto the utility of the salt in the invention and so also are the relativeamounts of the metal base and the oleophilic substance in the process bywhich the polymeric metal salt are made. The amounts of the reactantsare most conveniently described in terms of their chemical equivalents,based on the number of the functional groups present in the molecule.For instance, an oleophilic substance having one polar radical permolecule has one equivalent per mole (e.g., didodecyl benzene sulfonicacid). A Group I metal base having one metallic group per molecule hasone equivalent per mole; a Group I metal base having two metallic groupsper molecule has two equivalents per mole; a Group II metal base havingone metallic group per molecule has two equivalents per mole; and aGroup II metal base having two metallic groups per molecule has fourequivalents per mole; an oleophilic substance having two polar radicalsin the molecule has two equivalents per mole (e.g., a substitutedsuccinic acid or anhydride). The relative amounts of the metal and theoleophilic group in the polymeric metal salt are readily described byreference to the value of n in the structural formula, shown previously,describing the polymeric metal salt. In most instances, from 2 to about40 equivalents of the metal base per equivalent of the oleophilicsubstance is used in the process for preparing the polymeric metal salt.The preferred amount of the metal base is from about 4 to about 20equivalents per equivalent of the oleophilic substance.

An alternative method for preparing the polymeric metal salt involvespreparing an intermediate metalcontaining reactant by mixing the metalbase with a polar substance such as an alcohol or phenol with a promotersuch as an alcohol or a phenol illustrated above and treating theintermediate with an acidic gas such as carbon dioxide to convert iteither completely or partially to a carbonated complex and then mixingthe complex with the above-illustrated oleophilic substance. Thepreparation of the complex is preferably carried out in the presence ofa solvent or diluent such as mineral oil or the like and it may becarried out under anhydrous conditions or hydrous conditions dependingfor the most part on the oleophilic substance and the promoter used inthe process. In most instances the preparaion of the complex involves areaction temperature of from about 25C to the boiling point of thepromoter or the diluent which is usually below about 250C.

Various methods of introducing the metal salt into the combustion zoneof the engine are available. A convenient method is the injection of themetal salt as a powder into the combustion chamber. Another methodinvolves preparing a mixture of the fuel and the metal salt andinjecting the mixture into the combustion chamber. Another methodinvolves dissolving the metal salt in a carrier in which both the metalsalt and the fuel are soluble, dissolving the carrier and the metal saltin the fuel to prepare a solution and injecting the solution into thecombustion chamber. Still another method involves preparing a polymericmetal salt,

which is miscible with the fuel, dissolving the polymeric salt in thefuel and injecting the solution into the combustion chamber. ln the lastthree methods, the metal salt is released in the desired form at thetime when combustion of the fuel takes place. Other methods may beemployed provided that they resultin introducing the metal salt into thecombustion chamber and releasing it in the desired, finely divided formduring combustion.

The improved process of operating diesel engines of this invention isillustrated as follows: A single cylinder, four-stroke diesel engine isoperated at 1,200 rpm and under a load of 18-20 brake-horsepower on adiesel fuel having a sulfur content of 0.4 percent. The engine isequipped with an injector adapted for the injection of the smokesuppressing agent into the combustion chamber through the air in-takeopening. The engine is further equipped with a smoke spot" apparatus formeasuring the black exhaust smoke by allowing the exhaust gas to passthrough a white filter paper in a sampling tube. In each series oftests, after a break-in operation to establish equilibrium conditions,the engine is operated on the diesel fuel, without a smoke suppressingagent, until a constant Smoke Spot Rating is obtained in one minute(usually within 4.5-7.5) (by comparing the filter paper with a set ofstandards, i.e., papers having various amounts of deposits and graded ona numerical scale of to 10, 0 being indicative of no deposit and beingindicative of heavy deposit). The engine is then operated while thesmoke suppressing agent is injected into the combustion chamber untilequilibrium conditions are again established. After 20 seconds ofoperation and while the smoke suppressing agent is injected into thecombustion chamber, the exhaust gas is allowed to pass through thefilter paper for a period of one minute. The smoke spot rating of theengine is then noted and compared with the rating obtained without theuse of the smoke suppressing agent. The higher the rating, thegreaterthe tendency of the engine to form smoke. A number of metal saltshave been evaluated as the smoke suppressing agent in the above-notedprocess and their effectiveness is shown by the results of Table lbelow.

TABLE 1 Test Smoke Size Concentration Smoke Spot Series suppressing(micron) (by weight) Rating Agent l-a None l-b CaCOJ 4474 0.73% 4.5 I-cCaCO 74-449 087% 4.5 l-d CaCO l49-l77 0.73% 4.5 l-e CaCO 44 0.96% 3.5[La None 6.5 ll-b 8e50,, 44-74 2.18% 3 .5

TABLE l-Continued Test Smoke Size Concentration Smoke Spot Seriessuppressing (micron) (by weight) Rating Agent lI-c BaSO 250-297 2.55%4.5

ll-d BaCO, 44 2,85% 25 ll-e BaCO, 44 0.52% 4.5

ll-f BaCO; 250-297 3.92% 3.5

The improved process of operating diesel engines of this invention isfurther illustrated as follows: A singlecylinder, four-stroke dieselengine is operated at 1,200 rpm and under a load of l8-20brake-horsepower on a diesel fuel having a sulfur content of 0.4percent. The engineis equipped with a smoke spot apparatus such as isdescribed previously. In each series of tests, the engine is operated onthe diesel fuel without a smoke suppressant agent until equilibriumconditions are established and the smoke spot rating is noted. Theengine is then operated on the diesel fuel in which there ismechanically dispersed a powdered smoke suppressant agent. The engine isthen operated until equilibrium conditions are again established. Thesmoke spot rating of the engine is then noted and compared with therating obtained without the use of the smoke suppressant agent. Thehigher the rating, the greater the tendency of the engine to form smoke.A number of metal salts have been evaluated as the'smoke suppressantagent in this process and their effectiveness is shown by the results ofTable ll below.

The improved process of operating diesel engines of this invention isfurther illustrated as follows: A single cylinder, four-cycle dieselengine is operated under the following conditions: engine speed, 1,500 i10 rpm; fuel rate, 2.7 $0.04 lbs. per hour; and fuel, No. 2 diesel fuelhaving a sulfur content of 1 percent. The engine is equipped with asmoke tube apparatus for measuring the black exhaust smoke by allowingthe exhaust gas to pass through a glass tube (outside diameter of 0.7inch) in which the smoke is collected on the inside wall of the tube.The efiectiveness of the additive to prevent the formation of blacksmoke is rated by comparing the tube with a set of standard tubes havingvarious amounts of deposits and rated on a numerical scale of from 0 to8, 0 being indicative of no deposit and 8 being indicative of heavydeposit. The engine is also equipped with a smoke spot apparatus such asdescribed previously. After a break-in operation to establishequilibrium conditions, the engine is operated on the base fuel, withoutthe smoke suppressing agent, until a constant Smoke Spot Rating isobtained (usually within the range of from 8.5 to 9.0) and a constantSmoke Tube Rating is obtained (usually within the range of from 6.0

to 6.5). The engine is then operated on the diesel fuel in which thereis incorporated a polymeric metal salt (by dissolving the metal salt inthe fuel). The polymeric metal salt is released during combustion in theform of finely divided particles having an average particle size of lessthan 100 microns. After equilibrium conditions are again established,the Smoke Tube Rating and the Smoke Spot Rating are recorded atspecified intervals. The performance characteristics of the test fuelsare shown by the results of Table III.

The test fuels are prepared by blending No. 2 diesel fuel with a mineraloil concentrate of a polymeric metal salt identified as follows: (allpercentages are by weight unless otherwise specified):

Fuel A: Base fuel, i.e., No. 2 diesel fuel.

Fuel B: Base fuel containing 0.25 percent of a polymeric salt preparedby the procedure: A mixture of 730 parts (0.5 equivalent) of a neutralcalcium bright stock sulfonate, 58 parts (0.3 equivalent)ofheptylphenol, 57 parts of water, and 300 parts of toluene is heated to70C whereupon 123 parts 1.6 equivalents) of barium oxide is added over aperiod of 15 minutes. The mixture is then heated to 150C and carbonatedat the rate of 15 cubic feet per hour until carbon dioxide is no longerabsorbed by the reaction mixture. The mixture is filtered and thefiltrate is the desired basic barium sulfonate having a barium sulfateash content of 17.3 percent, a metal ratio of 2.9, and a reflux basenumber of 5 8.

Fuel C: Base fuel containing 0.32 percent of a polymeric salt preparedby the procedure: A calcium phenate is prepared by the followingprocedure. A mixture of 2,250 parts of mineral oil, 960 parts (5 moles)of heptylphenol, and 50 parts of water is stirred at 25C. The mixture isthen heated to 40C and 7 parts of calcium hydroxide and 231 parts (7moles) of 91 percent paraformaldehyde is added over a period of 1 hour.After heating the mixture to 80C., 200 additional parts of calciumhydroxide (making a total of 207 parts or 5 moles) is added over aperiod of 1 hour whereupon the mixture is heated to 150C and maintainedat that temperature for 12 hours while nitrogen is blown through themixture to assist in the removal of water. If foaming is encountered, afew drops of polymerized dimethyl silicone foam inhibitor may be addedto control the forming. The reaction mass is then filtered and thefiltrate, a 33.6 percent oil solution of the desired calcium phenate ofheptylphenol-formaldehyde condensation product, is found to contain 7.56percent of calcium A sulfate ash. A mixture of 1,000 parts of a neutralcalcium bright stock sulfonate having a calcium sulfate ash content of4.68 percent (60 percent mineral oil), 1207 parts of mineral oil, and158 parts of the calcium phenate prepared above, 240 parts of anisobutyl-amyl alcohol mixture (65:35 mole per cent), 108 parts ofmethanol and 170 parts of calcium hydroxide is prepared. The mixture isstirred at 45C and 50 parts of carbon dioxide is introduced over aperiod of 2 hours. thereafter, 3 additional portions of calciumhydroxide, each amounting to 1 14 parts, are added and each suchaddition is followed by the introduction of carbon dioxide as previouslyillustrated. A fourth portion, 1 14 parts, of calcium hydroxide is thenadded and 100 parts of carbon dioxide is added as above. This is thenfollowed by the addition of another 1 14 parts of calcium hydroxide and75 parts of carbon dioxide. The mixture is then heated to 150C in 3.5hours and maintained at this temperature while blowing with nitrogen for4 hours. A filter aid is added and the mixture is filtered. The filtrateis the desired product having a calcium sulfate ash content of 39.4percent and a metal ratio of 28.4.

Fuel D: Base fuel containing 0.5 percent of a polymeric salt prepared bythe procedure: A mixture of 5,049 parts (3.5 equivalents) of a neutralcalcium bright stock sulfonate having a calcium sulfate ash content of4.68 percent (60 percent mineral oil), 401 parts (2.1 equivalents) ofheptylphenol, and 342 parts of water is heated to C whereupon 1,725parts (22.4 equivalents) of barium oxide is added over a period of 2.5hours. The mixture is heated to 150C and carbonated until its basenumber (phenolphthalein indicator) is reduced to 8.4. lso-octyl alochol(170 parts) and 1,000 parts mineral oil is added to the mixture which isthen heated to 170C with stirring to remove the water. The mixture isfiltered and the filtrate is the desired basic barium bright stocksulfonate having a barium sulfate ash content of 23.7, a metal ratio of4.3, and a reflux base number of 91.

Fuel E: Base fuel containing 0.5 percent of a polymeric salt prepared bythe procedure: A basic calcium bright stock sulfonate having a bariumsulfate ash content of 28.5 and a metal ratio of 17.6 is preparedaccording to the procedure of Fuel C. A mixture of 2,000 parts of thisbasic sulfonate, 126 parts of iso-octyl alcohol, 168 parts of methanol,and 134 parts of calcium hydroxide is heated to 46C and carbonated with50 parts of carbon dioxide over a period of 2 hours. An additional 134parts of calcium hydroxide is added followed by carbonation with partsof carbon dioxide. The mixture is then heated to 157C/l 3-46 mm. andblown with nitrogen for 3 hours to remove the volatile materials. Filteraid is added and the mixture is filtered. The filtrate is the desiredbasic calcium bright stock sulfonate having a calcium sulfate ashcontent of 36.9.and a metal ratio of 35.

Fuel F: Base fuel containing 0.65 percent of a polymeric salt preparedby the procedure: A mixture of 61 parts of heptylphenol and 1,000 partsby weight of a chlorinated polyisobutene having a chlorine content of4.3 percent, prepared from a polyisobutene with a molecular weight of1,000, is heated to reflux (99C) and l 10 parts of phosphorustrichloride is added. Heating is continued until the reflux temperaturereaches 200C (in four hours). An additional 1 10 parts of phosphorustrichloride is then added and the mixture is heated at 200C for 6 /2hours, and then blown with nitrogen at 180200C for two hours. Thephosphorized polymer thus obtained is hydrolyzed by treatment with steamat 160C for three hours. The resulting hydrolyzed material haBHSsbhbiuscontenT 'of'figrht and a chlorine content of 0.3 percent. A basic bariumsalt is prepared by carbonating a mixture of 270 parts of mineral oil,18 parts of water, 143 parts of the phosphorized acid produced asdescribed above, 38 parts of heptylphenol and 140 parts of barium oxideat l30l40C until the mixture is substantially neutral tophenolphthalein. The mixture is dried by blowing with nitrogen at C andis diluted with mineral oil to a barium sulfate ash content of 25percent. The final solution contains 0.41 percent phosphorus and has areflux base number of 107 and a metal ratio of 8.3.

Fuel G: Base fuel containing 0.42 percent of a polymeric salt preparedby the procedure: A mineral oil solution of calcium bright stocksulfonate (4 equivalents) is mixed with heptylphenol (2.4 equivalents),water and barium oxide (19.2 equivalents) and treated with carbondioxide at 150C in the presence of a catalytic amount of barium chlorideuntil the base number of the mixture is 80 (phenolphthalein indicator).The product is filtered and the filtrate is an oil solution of apolymeric metal salt having a barium sulfate ash content of 26.42percent and a reflux base number of 104. The polymeric metal salt thuscontains 4.6 equivalents of metal per equivalent of the oleophilic groupderived from a bright stock sulfonate.

Fuel H: Base fuel containing 1.3 percent of a mixture of two polymericmetal salts: The one polymeric metal salt is that of Fuel C and theother polymeric metal salt is obtained by treating a mixture of a bariummahogany sulfonate (1 equivalent) and barium hydroxide (1.34equivalents) with carbon dioxide at 94-150C.

Fuel 1: Base fuel containing 0.35 percent of a polymeric salt preparedas follows: A mixture of 1,000 parts by weight of a polyisobutene havinga molecular weight of 1,000 and 90 parts by weight of phosphoruspentasulfide is heated to 260C over five hours and is then maintained atthat temperature for an additional five hours,,in an atmosphere ofnitrogen. It is then cooled to 150C and blown with steam for 5 hours.The resulting phosphorized-hydrolyzed material has a phosphorus contentof 2.35 percent and a sulfur content of 2.75 percent. A suspension ofbarium hydroxide in mineral oil is prepared by mixing 2,200 parts of oilwith 1,150 parts of barium oxide and blowing the mixture with steam forthree hours at a temperature of about 150C. To the barium hydroxidesuspension is added, at l45150C., 1,060 parts of the phosphorized acidprepared as described above. The addition is complete in three hours.After mixing for 30 minutes, 360 parts of heptylphenol is added overlhours at 150C. The resulting mixture is blown with carbon dioxide forfour hours at 150C., after which 850 parts of oil is added and thematerial is dried by blowing with nitrogen. The dried material isfiltered and the filtrate is diluted with mineral oil to a bariumsulfate ash content of percent. The product has a phosphorus content of0.38 percent. a sulfur content of 0.48 percent, a reflux base number of103 and a metal ratio of 8.6.

Fuel .1: Base fuel containing 0.65 percent of a polymeric metal saltprepared as follows: A suspension of 311 parts by weight of bariumhydroxide in 485 parts of mineral oil is-heated to 140150C., and 300parts of a phosphorized and hydrolyzed acid prepared as described inFuel 1 is added over a 1-hour period. Heptylphenol, 153 parts, is addedover one-half. hour and the mixture is then blown with carbon dioxidefor 2.3 hours at 150-155C. At the end of this time, 181 parts of bariumhydroxide is added over minutes and carbonation is continued. Anadditional 181 parts of barium hydroxide is added two hours later.Carbon dioxide addition is continued for 2% hours, and finally 274 partsof mineral oil is added. The solution is dried by blowingnitrogenzthrough at a temperature of 150C and is then filtered. Afterfiltration, mineral oil is added to dilute the solution to a bariumsulfate ash concentration of 38.5 percent. The product thus obtained hasa phosphorus content of 0.35 percent, a sulfur content of 0.38 percent,a reflux base number of 168 and a metal ratio of 14.2.

Fuel K: Base fuel containing 0.36 percent of a polymeric metal saltprepared by treating a mixture of a polyisobutene (molecular weight of1,000)-substituted succinic anhydride (0.81 equivalent), heptylphenol 1equivalent), and barium hydroxide (9.8 equivalents) with carbon dioxide.

Fuel L: Base fuel containing 0.294 percent of a polymeric metal saltprepared by treating a calcium mahogany sulfonate and calcium hydroxidel4 equivalents of calcium per equivalent of mahogany sulfonate) withcarbon dioxide in the presence of an alcohol mixture as the promoter(mixture of methyl, isobutyl, and pentyl alcohols).

Fuel M: Base fuel containing 1.19 percent of a polymeric metal saltprepared by treating a mixture of a hydrolyzed reaction product (1.66equivalents) of polyisobutene (molecular weight of 1,000) and phosphoruspentasulfide, and heptylphenol (1 equivalent) and barium hydroxide (5.1equivalents) with carbon dioxide.

Fuel N: Base fuel containing 1.19 percent of a polymeric metal saltprepared as follows: A mixture of 2,140 parts by weight of polyisobutenehaving a molecular weight of 1,000 and 317 parts of phosphoruspentasulfide is heated to 232C over a 5-hour period and maintained at232237C for five hours. Steam is then passed through the mixture at232-237C for thirteen hours. The phosphorized product is dried byblowing with nitrogen at 232C for one hour. A suspension of 314 parts ofbarium oxide in 950 parts of mineral oil is blown with steam for 2%hours. The phosphorized product prepared as described above is addedover a 3-hour period, at a temperature of l35140C. The reaction mixtureis blown with steam at this temperature for one hour and an additional592 parts of mineral oil is added. Water is removed by blowing withnitrogen at 150C for 2 hours, after which the reaction mixture isfiltered. To a mixture of 855 parts of the barium salt produced asdescribed above, 321 parts of oil and 82 parts of heptylphenol, at atemperature of C., is added 216 parts of barium oxide over a 30-minuteperiod. The reaction mixture is blown with steam for 2% hours, and thenwith carbon dioxide for 5% hours, at a temperature of -140C. Water isremoved by blowing with nitrogen at 150-155C for 5 hours and thematerial is filtered. The filtrate is diluted with oil to a bariumsulfate ash concentration of 21 percent. The product produced by theabove method contains 0.9 percent phosphorus and 0.35 percent sulfur,has a reflux base number of 72 and a metal ratio of 3.0.

Fuel 0: Base fuel containing 1.16 percent of a polymeric metal saltprepared as follows: A chlorinated polyethylene oil (molecular weight610) containing 4.3 percent chlorine is phosphorized by the followingprocedure. One mole (610 grams) of the oil is heated to 100C andone-half of a 137.5-gram (1 mole) portion of phosphorus trichloride isadded. The reaction mixture is heated to 210C over a 14-hour period,while the remainder of the phosphorus trichloride is added slowly. About20 grams of unreacted phosphorus trichloride is removed at 180C/20 mm.To the reaction mixture is added 305 grams of mineral oil, and themixture is blown with steam for two hours at -l60C and then dried atC/30 mm. A mixture of 420 grams of the phosphorized-hydrolyzed materialthus obtained, 66 grams of heptylphenol, 347 grams of mineral oil and 25grams of water is heated to 70C and 21 1 grams of barium oxide is addedin small increments over 30 minutes. The mixture is heated to 150C andblown with carbon dioxide until a neutral product is obtained. Theproduct is then filtered. The filtrate contains 26.4 percent bariumsulfate ash and 0.53 percent phosphorus, and has a metal ratio of 6.6.

Fuel P: Base fuel containing 0.97 percent of -a polymeric metal saltprepared as follows: A mixture of 800 grams of polyethylene (molecularweight 2,500) and 25.6 grams of sulfur is heated to 160C. To the mixtureis added, over 45 minutes, 88 grams of phosphorus trichloride. Thereaction mixture is heated for seven hours at l60-l65C., after which thepressure is reduced to 30 millimeters and 31 grams of PSCl is removed bydistillation. To the remaining material is added 400 grams of mineraloil, and the mixture is blown with steam for one hour at 150C. It isthen heated at 150C/30 mm. to remove water and filtered. To 840 grams ofthe phosphosulfurized product obtained as described above are added 132grams of heptylphenol, 300 grams of mineral oil and 50 grams of water.The mixture is heated to 70C and 423 grams of barium oxide is added. Themixture is then heated to 150C over about 1 /2 hours and is blown withcarbon dioxide until it becomes slightly acidic. During the carbondioxide treatment, 50 grams of isooctyl alcohol is added to decrease theviscosity of the mixture. An additional 300 grams of mineral oil is thenadded and the solution is filtered. The filtrate contains 0.25 percentphosphorus and 22.69 percent barium sulfate ash, and has a metal ratioof 12.1.

Fuel Q: Base fuel containing 1.38 percent of a polymeric metal saltprepared by treating a mixture of a hydrolyzed reaction product (0.0353equivalent) of a polyisobutene (molecular weight of 1,000) andphosphorus pentasulfide, heptylphenol (1 equivalent) and barium oxide(6.6 equivalents) with carbon dioxide.

The polymeric salts include especially those described in co-pendingapplications Ser. No. 665,934, filed Sept. 6, 1967, now abandoned; Ser.No. 474,497, filed July 23, 1965, now abandoned; and Ser. No. 486,558,filed Sept. 10, 1965 now abandoned. The specification of each of saidco-pending applications is hereby incorporated by reference in thepresent specification. The polymeric salts in which the oleophilic groupis derived from a bright stock sulfonic acid, such as are described ineo-pending application Ser. No. 665,934, are characterized by an unusualability to impart emulsion resistance to fuels. The emulsion resistanceof the metal compositions of this invention is shown by the resultsshown in Table IV, of an Emulsibility Test. The test consists ofpreparing a mixture of cc of a diesel fuel and 1 cc of water, placing itin a 4-ounce, square glass bottle (width and depty dimension of 1% X 1%inches), homogenizing the mixture, and then allowing the mixture tostand at room temperature to allow a separation of the water layer andthe fuel layer. At the end of periods of standing of 5 minutes, 3 hours,6 hours, and 24 hours, the sample is inspected for turbidity by placinga newspaper print behind the bottle and viewing it through the fuellayer of the sample. The turbidity is then rated on a numerical scalefrom 0 to 3, 0 being indicative of a clear sample (i.e., completeseparation of the water layer and the fuel layer) and 3 being indicativeof cloudiness of the sample to the extent that the newspaper print iscompletely illegible. A lower rating indicates a higher emulsionresistance. The fuel used in the test is a No. 2 diesel fuel. Forpurpose of comparison, a commerical barium mahogany sulfonate detergentis also tested and its great tendency to promote emulsion of water andfuel is shown by the results in Table IV.

TABLE IV Water Retention Test An especially effective additivecombination consists of a polymeric metal salt described in co-pendingapplication Ser. No. 486,558, i.e., in which the oleophilic group isderived from an acidic phosphorized aliphatic oraliphatically-substituted aromatic hydrocarbon, and another polymericmetal salt in which the oleophilic group is derived from an oil-solublesulfonic acid. The latter is exemplified by a carbonated calciumsulfonate with a high metal ratio such as is prepared by reacting anoil-soluble sulfonic acid or a neutral calcium sulfonate with an excessof a calcium base such as calcium oxide or hydroxide or alcoholate andcarbonating the mixture in the presence of a promoter such as a phenoliccompound or an alcohol described previously.

More specifically, it has been found that the tendency of a diesel fuelto form smoke is very effectively suppressed by adding to said fuelabout 0.01-5 percent by weight of a combination of l a basic alkalineearth metal salt of an acidic phosphorized hydrocarbon and (2) asubstantially neutral, carbonated calcium sulfo- A nate complex having ametal ratio of at least about 10.

Such carbonated calcium sulfonates with high metal ratios may beprepared by the method described in copending application Ser. No.309,293, filed Sept. 16, 1963. Briefly, this method comprises reacting acarbonated calcium sulfonate complex having a metal ratio of about1.1-8.0 with a calcium base in the presence of an number of equivalentsof the calcium base to the calcium sulfonate complex being at leastabout :1, and then treating the mixture with carbon dioxide to a basenumber below about 20 and heating to drive off volatile constituents(e.g., alcohol and water). The following examples are typical.

EXAMPLE 1 Part A One thousand parts of a 51 percent mineral oil solutionof neutral sodium mahogany sulfonate having a sodium sulfate ash contentof 8.5 percent is heated to 95-l00C. with stirring, and a solution of71.3 parts of calcium chloride in 84 parts of water is added. Stirringand heating are continued for two hours, and then 72 parts of lime isintroduced. After an additional two hours of stirring at 95-100C. toremove most of the water, the oil solution is cooled to 48C. and 130parts of methanol is added. The mixture is blown with carbon dioxide at43-48C. to a base number of 4-8, heated to 150C. to remove the methanoland remaining water, and filtered. Part B A mixture of 960 parts ofheptylphenol, 2,250 parts of mineral oil and 50 parts of water is heatedto 40C. and 231 parts of paraformaldehyde is added over 45 minutes,followd by 6.6 parts of lime. The mixture is heated to 80-89C. andcharged with an additional 200 parts of lime over 45 minutes. Water isremoved at 150C. by blowing with nitrogen, 50 parts of filter aid isadded and the product is filtered. Part C A mixture of 15,972 parts ofthe carbonated calcium sulfonate of Part A, 804 parts of the calciumheptylphenate of Part B, 5,000 parts of mineraloil, 2,800 parts ofmethanol and 1,405 parts of a mixture of 64 percent (by weight) isobutylalcohol and 36 percent amyl alcohol is heated to 46C., with stirring,and 1,490 parts of lime are added. The mixture is then blown with carbondioxide at 42.-52C. until a direct base number between 40 and 50 isattained. Three additional 1,490- part portions of lime are successivelyintroduced, each one being followed by carbon dioxide treatment. in thefinal CO treatment, the direct base number is lowered to 35-45. Alcoholand water are removed by stripping at 80l55C., and the residue isfiltered in the presence of a filter aid. The product has a calciumsulfate ash content of 40.0 percent.

Example 2 To a mixture of 1,685 parts of the. calcium sulfonate ofExample 1, Part A; 84 parts of the calcium phenate of Example 1, Part B;and 559 parts of mineral oil,is added 157 parts of lime. The mixture isheated with stirring at 50C., and 148 parts of a mixture of 64 percent(by weight) isobutyl alcohol and 36 percent amyl alochol and 296 partsof methanol are added. Carbon dioxide is passed through the mixture fortwo hours and then three more 157-part portions of lime are introduced,with carbon dioxide treatment for 3% hours following the addition ofeach portion. The volatile material is then removed by stripping atabout 160C. and the product is filtered. The material thus obtained hasa calcium sulfate ash content of 43 percent.

What is claimed is:

l. A combustion process involving the burning of a diesel or jet fuel inan internal combustion engine tending to produce smoke, comprisingburning said fuel in the presence of a black exhaust smoke-reducingamount of a basic metal-containing composition having wherein M is aGroup I or Group 11 metal, Y is carbonyl group, n is greater than 1, Ais an oleophilic anionic group having at least about eight aliphaticcarbon atoms and B is a chain ending group selected from the groupconsisting of hydrogen or -MA where M and A are as previously defined.

2. The process of claim 1 wherein M is barium and Y is carbonyl.

3. The process of claim 1 wherein M is calcium and Y is carbonyl.

4. The process of claim 1 wherein the basic metalcontaining compositionhas the formula A MO -o) B an amount of at least about 0.01 percent byweight to 5 percentby weight of the fuel.

5. The process of claim 4 wherein the oleophilic group is derived from ahydrocarbon sulfonic acid having at least about 12 aliphatic carbonatoms in the hydrocarbon radical.

6. The process of claim 1 which comprises operating the engine on adiesel or jet fuel having incorporated therein from about 0.01 to about5 percent by weight of an oil-soluble, carbonated basic alkaline earthmetal salt of a bright stock sulfonic acid..

7. The process of claim 6 wherein the alkaline earth metal salt is acalcium salt.

8. The process of claim 6 wherein the alkaline earth metal salt is abarium salt.

9. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a bright stock sulfonic acid,

B. a promoter selected from the class consisting of alcohols, phenols,calcium phenates, mercaptans, aci-nitro compounds and enolic compounds,and

C. more than one equivalent of an alkaline earth metal base perequivalent of (A),

at a temperature of from about 25C. to the boiling point of the mixture,and thereafter heating the carbonated mixture to remove the volatilecomponents.

10. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a bright stock sulfonic acid,

B. an alcohol, and

C. more than one equivalent of an alkaline earth metal base perequivalent of (A),

at a temperature of from about 25C. to the boiling point of the mixture,and thereafter heating the carbonated mixture to remove the volatilecomponents.

l l. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a bright stock sulfonic acid,

B. a phenol, and

C. more than one equivalent of barium or calcium hydroxide perequivalent of (A),

at a temperature of from about 25C. to the boiling point of the mixture,and thereafter heating the carbonated mixture to remove the volatilecomponents.

12. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a bright stock sulfonic acid,

B. from about 0.10 to about 10 equivalents per equivaient of (A), of analcohol having less than about 12 carbon atoms, and

C. more than one equivalent of barium or calcium hydroxide perequivalent of (A), at a temperature of from about 25C. to the boilingpoint of the mixture, and thereafter heating the carbonated mixture toremove the volatile components.

I 13. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a bright stock sulfonic acid,

B. from about 0.25 to about 10 equivalents per equivalent of (A), of analcohol having less than about 12 carbon atoms, and

C. more than one equivalent of barium oxide per equivalent of (A),

at a temperature of about 25C. to the boiling point of the mixture andthereafter heating the carbonated mixture to remove the volatilecomponents.

14. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a neutral calcium salt of a bright stock sulfonic acid,

B. from about 0.25 to about 10 equivalents of heptylphenol perequivalent of (A), and

C. more than one equivalent of barium oxide per equivalent of (A),

at a temperature of from about 25C. to the boiling point of the mixture,and thereafter heating the carbonated mixture to remove the volatilecomponents.

15. The process of claim 6 wherein the alkaline earth metal salt isprepared by the process which comprises carbonating a mixture comprisingA. a neutral calcium salt of a bright stock sulfonic acid,

B. from 0.25 to about 10 equivalents per equivalent of (A), of a mixtureof an alcohol and a calcium phenate of a heptylphenolformaldehydecondensation product, the calcium phenate comprising up to 70 percent byweight of the mixture, and

C. more than one equivalent of barium oxide per equivalent of (A),

at a temperature of about 25C. to the boiling point of the mixture andthereafter heating the carbonated mixture to remove the volatilecomponents.

16. A fuel for use in diesel or jet engines which contains about 0.01-5percent by weight of a basic alkaline earth metal salt of an acidicphosphorized aliphatic or alkylaromatic hydrocarbon having a molecularweight of about ISO-48,000.

17. A fuel for use in diesel or jet engines which contains about 0.01-5percent by weight of a basic alkaline earth metal salt of an acidicphosphorized aliphatic hydrocarbon having a molecular weight of aboutl5048,000; said salt being prepared by the process which comprisescarbonating a mixture comprising A. an acidic phosphorized aliphatichydrocarbon having a molecular weight of about ISO-48,000;

B. a promoter selected from the group consisting of alcohols, phenols,amines and mercaptans; and

C. more than one equivalent of an alkaline earth metal base perequivalent of (A); and thereafter heating the carbonated mixture toremove volatile constituents.

18. The fuel of claim 17 wherein the alkaline earth metal is barium.

19. The fuel of claim 18 wherein the aliphatic hydrocarbon is apolyisobutene.

20. In a method for operating a diesel or jet engine, the improvementwhich comprises burning a diesel or jet fuel having incorporated thereinabout 0.01-5 percent by weight of a basic alkaline earth metal salt ofan acidic phosphorized aliphatic or alkylaromatic hydrocarbon having amolecular weight of about ISO-48,000, thereby suppressing the tendencyof said engine to form black exhaust smoke by improper combustion ofsaid fuel.

21. in a method for operating a diesel or jet engine according to claim20, the improvement which comprises buming a diesel or jet fuel havingtherein about 0.01-5 percent by weight of a basic alkaline earth metalsalt of an acidic phosphorized aliphatic hydrocarbon, which salt isprepared by the process which comprises carbonating a mixture comprisingA. an acidic phosphorized aliphatic hydrocarbon having a molecularweight of about ISO-48,000;

B. a promoter selected from the group consisting of alcohols, phenols,amines and mercaptans: and

C. more than one equivalent of an alkaline earth metal base perequivalent of (A); and thereafter heating the carbonated mixture toremove volatile constituents.

22. The method of claim 21 wherein there is also incorporated into thefuel about 0.0l-5 percent of a substantially neutral, carbonated calciumsulfonate complex having a metal ratio of at least about 10, saidcomplex being prepared by reacting a carbonated calcium sulfonatecomplex having a metal ratio of about 1.l8.0 with a calcium base in thepresence of an oilsoluble calcium phenate and an aliphatic monohydricalcohol, or mixture of such alcohols, the ratio of the number ofequivalents of said calcium base to said calcium sulfonate complex beingat least about 10:1; treating the mixture thus formed with carbondioxide to a base number below about 20, and heating to drive offvolatile constituents.

, UNiTth STATES PATENT OFFECE CERTH ECATE 0F CCRRECTION lnventm-(s)William Mom'oo Jul-111ml" It is certified that error appears in theabove-idehtified patent and that said Letters Patent are herebycorrected as shown below:

At column 16, line 1Z9, that is Claim 9, line t, "A, should be --(A)--;line 50, that is Claim 9, line 5, "B; should be --(B)--; line 53, thatis Claim 9, line 8, "0." should be --(c line 61, that is Claim 10, linet, "A should, be --(A)--; line 62, that is Claim 10, line 5, "B. shouldbe --(B)--; line 63, that is Claim 10, line 6, *0. should be --(c)--.

I At column 17, line 4, that is Claim 11, line t, "A. should be (14);line 5, that is Claim ll, line 5, "13. should be --(B)--; line 6, thatis Claim ll, line 6, "g." should be --(c)--, line 14, that is Claim 12,line .4, A. should be --EA line 15, that is Claim 12, line 5, "B. shouldbe B)--, line 18, that is Claim 12,- line 8, "C. should be c)--, lihs26, that claim 13, line 4, "A." should be A)--; lihe27, that is Claim15, line "B." should; be B)--; line 50, that is Claim 15, line 8, "c.should be --(c line 58, that is Claim 14, line 4, "A. should'he --(A)--,line 40, that is Claim 14, line 6, "B." should be figs); line 42, thatis Claim 14, line 8, "c. should be c)--; line 50, that is Claim 15, line4, "A. should'be --(A)--; line 52, that is Claim 15, line 6, "B. shouldbe figs line 57, that is Claim 15, line 11, "0. should be 3 At column18, line ll, that is Claim 17, line 7, "A should be -(A)--; line 13,that is Claim 17, line 9, "B. should be --(B)--; line 15, that is Claim17, line ll, "C. should be -(c line 59, that is Claim 21, line 8, "A."should be --(.A)--; line 41-, that is Claim 21, line 10, "B. should beis line 45, tha is Claim 21, line 12, "a." hould be FORM PC40 VUSCOMM-DC 60376-P69 Q U.S. GOVERNMENT PRINTING OFFICE 2 I969 0-3$6'3Sl.

. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION March 19, 197

Patent No. 5:79 v Dated Inventor(s) William Monroe LeSuer It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Under Related U.S Application Data line 5, "Ser. No. i,55 should be--Se1" No. 486,558--; line 8, "Sept. 5, 192 should be --Sept. 5, 196%.

Signed and sealed this 1st day of October 1974,

(SEAL) Attest:

MCCOY M; GIBSON JR. 0. MARSHALL DANN Attesting Officer Commissioner ofPatents USCOMM-DC 50376-P69 U.S. GOVERNMENT PRINTING OFFICE I900 O3S6-3!4.

F OFIM PO-I 050 (10-69)

2. The process of claim 1 wherein M is barium and Y is carbonyl.
 3. Theprocess of claim 1 wherein M is calcium and Y is carbonyl.
 4. Theprocess of claim 1 wherein the basic metal-containing composition hasthe formula
 5. The process of claim 4 wherein the oleophilic group isderived from a hydrocarbon sulfonic acid having at least about 12aliphatic carbon atoms in the hydrocarbon radical.
 6. The process ofclaim 1 which comprises operating the engine on a diesel or jet fuelhaving incorporated therein from about 0.01 to about 5 percent by weightof an oil-soluble, carbonated basic alkaline earth metal salt of abright stock sulfonic acid.
 7. The process of claim 6 wherein thealkaline earth metal salt is a calcium salt.
 8. The process of claim 6wherein the alkaline earth metal salt is a barium salt.
 9. The processof claim 6 wherein the alkaline earth metal salt is prepared by theprocess which comprises carbonating a mixture comprising A. a brightstock sulfonic acid, B. a promoter selected from the class consisting ofalcohols, phenols, calcium phenates, mercaptans, aci-nitro compounds andenolic compounds, and C. more than one equivalent of an alkaline earthmetal base per equivalent of (A), at a temperature of from about 25*C.to the boiling point of the mixture, and thereafter heating thecarbonated mixture to remove the volatile components.
 10. The process ofclaim 6 wherein the alkaline earth metal salt is prepared by the processwhich comprises carbonating a mixture comprising A. a bright stocksulfonic acid, B. an alcohol, and C. more than one equivalent of analkaline earth metal base per equivalent of (A), at a temperature offrom about 25*C. to the boiling point of the mixture, and thereafterheating the carbonated mixture to remove the volatile components. 11.The process of claim 6 wherein the alkaline earth metal salt is preparedby the process which comprises carbonating a mixture comprising A. abright stock sulfonic acid, B. a phenol, and C. more than one equivalentof barium or calcium hydroxide per equivalent of (A), at a temperatureof from about 25*C. to the boiling point of the mixture, and thereafterheating the carbonated mixture to remove the volatile components. 12.The process of claim 6 wherein the alkaline earth metal salt is preparedby the process which comprises carbonating a mixture comprising A. abright stock sulfonic acid, B. from about 0.10 to about 10 equivalentsper equivalent of (A), of an alcohol having less than about 12 carbonatoms, and C. more than one equivalent of barium or calcium hydroxideper equivalent of (A), at a temperature of from about 25*C. to theboiling point of the mixture, and thereafter heating the carbonatedmixture to remove the volatile components.
 13. The process of claim 6wherein the alkaline earth metal salt is prepared by the process whichcomprises carbonating a mixture comprising A. a bright stock sulfonicacid, B. from about 0.25 to about 10 equivalents per equivalent of (A),of an alcohol having less than about 12 carbon atoms, and C. more thanone equivalent of barium oxide per equivalent of (A), at a temperatureof about 25*C. to the boiling point of the mixture and thereafterheating the carbonated mixture to remove the volatile components. 14.The process of claim 6 wherein the alkaline earth metal salt is preparedby the process which comprises carbonating a mixture comprising A. aneutral calcium salt of a bright stock sulfonic acid, B. from about 0.25to about 10 equivalents of heptylphenol per equivalent of (A), and C.more than one equivalent of barium oxide per equivalent of (A), at atemperature of from about 25*C. to the boiling point of the mixture, andthereafter heating the carbonated mixture to remove the volatilecomponents.
 15. The process of claim 6 wherein the alkaline earth metalsalt is preparEd by the process which comprises carbonating a mixturecomprising A. a neutral calcium salt of a bright stock sulfonic acid, B.from 0.25 to about 10 equivalents per equivalent of (A), of a mixture ofan alcohol and a calcium phenate of a heptylphenolformaldehydecondensation product, the calcium phenate comprising up to 70 percent byweight of the mixture, and C. more than one equivalent of barium oxideper equivalent of (A), at a temperature of about 25*C. to the boilingpoint of the mixture and thereafter heating the carbonated mixture toremove the volatile components.
 16. A fuel for use in diesel or jetengines which contains about 0.01-5 percent by weight of a basicalkaline earth metal salt of an acidic phosphorized aliphatic oralkylaromatic hydrocarbon having a molecular weight of about 150-48,000.17. A fuel for use in diesel or jet engines which contains about 0.01-5percent by weight of a basic alkaline earth metal salt of an acidicphosphorized aliphatic hydrocarbon having a molecular weight of about150-48,000; said salt being prepared by the process which comprisescarbonating a mixture comprising A. an acidic phosphorized aliphatichydrocarbon having a molecular weight of about 150-48,000; B. a promoterselected from the group consisting of alcohols, phenols, amines andmercaptans; and C. more than one equivalent of an alkaline earth metalbase per equivalent of (A); and thereafter heating the carbonatedmixture to remove volatile constituents.
 18. The fuel of claim 17wherein the alkaline earth metal is barium.
 19. The fuel of claim 18wherein the aliphatic hydrocarbon is a polyisobutene.
 20. In a methodfor operating a diesel or jet engine, the improvement which comprisesburning a diesel or jet fuel having incorporated therein about 0.01-5percent by weight of a basic alkaline earth metal salt of an acidicphosphorized aliphatic or alkylaromatic hydrocarbon having a molecularweight of about 150-48,000, thereby suppressing the tendency of saidengine to form black exhaust smoke by improper combustion of said fuel.21. In a method for operating a diesel or jet engine according to claim20, the improvement which comprises burning a diesel or jet fuel havingtherein about 0.01-5 percent by weight of a basic alkaline earth metalsalt of an acidic phosphorized aliphatic hydrocarbon, which salt isprepared by the process which comprises carbonating a mixture comprisingA. an acidic phosphorized aliphatic hydrocarbon having a molecularweight of about 150-48,000; B. a promoter selected from the groupconsisting of alcohols, phenols, amines and mercaptans: and C. more thanone equivalent of an alkaline earth metal base per equivalent of (A);and thereafter heating the carbonated mixture to remove volatileconstituents.
 22. The method of claim 21 wherein there is alsoincorporated into the fuel about 0.01-5 percent of a substantiallyneutral, carbonated calcium sulfonate complex having a metal ratio of atleast about 10, said complex being prepared by reacting a carbonatedcalcium sulfonate complex having a metal ratio of about 1.1-8.0 with acalcium base in the presence of an oil-soluble calcium phenate and analiphatic monohydric alcohol, or mixture of such alcohols, the ratio ofthe number of equivalents of said calcium base to said calcium sulfonatecomplex being at least about 10:1; treating the mixture thus formed withcarbon dioxide to a base number below about 20, and heating to drive offvolatile constituents.